Water 2013, 5, 659-676; doi:10.

3390/w5020659
OPEN ACCESS

water
ISSN 2073-4441
www.mdpi.com/journal/water
Review

Ion Chromatographic Analyses of Sea Waters, Brines and

Related Samples
Nataša Gros

Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, SI-1000 Ljubljana,
Slovenia; E-Mail: natasa.gros@fkkt.uni-lj.si; Tel.: +386-1-2419-164; Fax: +386-1-2419-220

Received: 10 April 2013; in revised form: 14 May 2013 / Accepted: 20 May 2013 /
Published: 5 June 2013

Abstract: This review focuses on the ion chromatographic methods for the analyses of
natural waters with high ionic strength. At the beginning a natural diversity in ionic
composition of waters is highlighted and terminology clarified. In continuation a brief
overview of other review articles of potential interest is given. A review of ion
chromatographic methods is organized in four sections. The first section comprises articles
focused on the determination of ionic composition of water samples as completely as
possible. The sections—Selected Anions, Selected Cations and Metals—follow. The most
essential experimental conditions used in different methods are summarized in tables for a
rapid comparison. Techniques encountered in the reviewed articles comprise: direct
determinations of ions in untreated samples with ion- or ion-exclusion chromatography, or
electrostatic ion chromatography; matrix elimination with column-switching; pre-concentration
with a chelation ion chromatography and purge-and-trap pre-concentration. Different
detection methods were used: non-suppressed conductometric or suppressed conductometric,
direct spectrometric or spectrometric after a post-column derivetization, and inductively
coupled plasma in combination with optical emission or mass spectrometry.

Keywords: ion chromatography; sea water; brine; mineral water; anions; cations; metals

1. Natural Diversity of Waters

We restrict the scope of this review and choose to focus on natural waters with high ionic strength
in which concentrations of ions extend over several orders of magnitude and therefore these waters
present a special challenge for ion chromatographic (IC) analysis, especially if major and minor ions
Water 2013, 5 660

are to be determined simultaneously. Natural waters of different types differ not only in a total
concentration of dissolved solids (TDS) but also in concentration proportions between individual ions.
Awareness how diverse are natural waters is not widely shared. Carlé, in his monograph, compiled
the results of analyses of more than 700 Central European mineral and thermal waters [1]. An
electronic database prepared on the bases of this monograph enables an insight into natural diversity in
the ionic composition of waters [2]. One of the aspects of the natural diversity of waters are wide
concentration ranges, in which ions which are of interest for ion chromatographic analyses occur in
natural waters (Figure 1).

Figure 1. Concentration ranges of ions and other species which are of interest for ion
chromatographic analyses and were observed in the Central European mineral and
thermal waters [2].

γ (mg/L)
1000000

100000

10000

1000

100

10

0.1
H2SiO3
Li+
Na+
NH4+

Mg2+

Sr2+
F-
Cl-
Ca2+

NO2-

NO3-

HCO3-
SO4 2-

HBO2
K+

Br-

HPO4 2-

I-

CO3 2-

0.01

0.001

Fractions of the main cations and the main anions expressed in milliequivalent percent (meq%)
classify water types. In Figure 2, we present waters from Carlé monograph in the form of a Piper
diagram. As can be seen from the diagram, this limited set of water samples already well represents the
natural diversity of waters in spite of the fact that waters were from a fairly restricted geographic area.
The anionic triangle and a diamond are nearly uniformly covered in dots.
It has to be mentioned that there is some ambiguity in a usage of different terms related to waters. A
term mineral water was in the Central European and some Eastern European Countries traditionally
understood as a highly mineralized natural water containing TDS in a concentration at least equal to or
higher than 1 g/L. Mineral waters comprised not only waters suitable for drinking or bathing but also
brines of different types and of a potential industrial relevance, as it is also obvious from a Piper
diagram in which the right corner of the diamond is dedicated to brines, also called saline, and well
cowered in dots. Sea water with 77.1 meq% of sodium, 18.1 meq% of magnesium, 2.9 meq% of
calcium, 1.6 meq% of potassium, 90.9 meq% of chloride and 9.1 meq% of sulfate would have been
presented in this same corner of the diagram. Other corners of a diamond of a Piper diagram are
dedicated to waters of other distinctive types: the top corner comprises waters with a high permanent
Water 2013, 5 661

hardness, the left corner waters with a high temporary hardness and the bottom corner waters in which
alkali carbonates prevail.

Figure 2. Natural diversity in composition of the Central European mineral and thermal
waters. Brines are presented in the right corner of the diamond.

It has to be pointed out that an entirely different understanding of the term mineral water may be
prevailing in some Europe countries and many countries World-wide, where this term is frequently
used as a synonymous term for spring waters or ordinary drinking waters, usually bottled but not
highly mineralized. In this paper, we use a term with the previously described meaning.
In this review, we provide an overview of ion chromatographic methods developed for analyzing
sea waters, brines and other highly mineralized natural waters, e.g., mineral waters and oil-field
waters. As it will be presented in the continuation the great majority of applications described in
literature deal with ion chromatographic analyses of sea waters or brines, only very few are dedicated
to ion chromatographic analyses of mineral waters. One of the possible explanations would have been
their natural diversity. Even waters from the same aquifer and from the boreholes, which are not far
apart, can be of different types if the boreholes reach into a different section of the aquifer, and waters
Water 2013, 5 662

of different balneological types present distinctive analytical problems. A paper, which tried to give
some guidance in this area, demonstrated how ion chromatographic determinations of cations in 116
natural mineral waters can be reduced on only 14 distinctive analytical sub-cases [3].

2. Review Papers

Reviews which cover the topics are not included in this paper, but might be of a potential interest to
a reader, are briefly mentioned in this section.
The progress made in the field of ion chromatography has been reviewed from various points of
view. The most closely related to the topic of this paper is an early review of the suppressed ion
chromatographic analysis of anions in environmental waters containing high salt concentrations, which
was published in 1996 [4]. The aspect of determining metal pollutants in environmental matrices using
ion chromatography was covered by Shaw and Haddad [5].
Ion chromatographic analyses of ordinary drinking waters, tap or spring waters were presented by
Michalski [6], who also provided a brief and comprehensive account of the milestones in the
development of ion chromatography. Those more interested in the early development of the area can
find more detailed outlines written from two different angles in papers of Fritz [7] and Evans [8] while
Haddad et al focused on the development of the suppressor technology [9] and more recently on the
recent development and emerging directions in ion chromatography [10].
Paull and Nesterenko provided an overview of applications involving the novel ion chromatographic
stationary phases for ion chromatographic analyses of complex matrices [11]. Nakatani et al. presented
an overview of one of more recent challenges of ion-exclusion/ion-exchange chromatography in
determining simultaneously inorganic anions and cations [12]. Monolitic columns, which open up
some new opportunities for ion chromatography, were also reviewed [13,14].

3. Ion Chromatographic Analyses of Sea Waters, Brines and Related Samples

This review is divided into subsections in a similar way, as it is a common practice in reporting the
results of an extended water analysis, which among other sections usually at the beginning comprises
the following sections: anions, cations and metals.
Even though papers focusing on the determinations of a total ionic composition of waters with ion
chromatography as completely as possible are very few we start the overview with them, since they
well illustrate the potential of this analytical technique, and an anion-cation balance or a charge
balance is an important introductory analytical data quality check in any extended water analysis.

3.1. Total Anionic and/or Cationic Composition of Water

3.1.1. Anions and Cations

In ten natural mineral waters of different composition and different total mineralization F−, Cl−, Br−,
SO42−, I−, Na+, K+, Mg2+, Ca2+ were successfully determined within three runs on three different
columns, one for iodide, another for the remaining anions and the third for the cations. More details are
given in Table 1. Taking into account that NO3−, NO2− and HPO42− were not detected, 12 ions of the 20
usually included in an extended chemical analysis of natural waters were covered by ion
Water 2013, 5 663

chromatography alone representing at least 98.60% and up to 99.96% of total cation composition of
water samples and between 98.90% and 99.96% of the remaining anion composition after hydrogen
carbonate was determined titrimetricaly. Very good agreement of the anion-cation balance or a charge
balance was obtained for all mineral waters confirming an excellent performance of ion
chromatography for the basic and extended chemical analysis of highly mineralized water samples [15].
Typical chromatograms of a sample are in the original publication presented in Figure 3.

Table 1. Anionic and/or cationic composition of waters with high ionic strength
determined as completely as possible with ion chromatography.
Analyte/Sample Column Eluent Detection Reference
1 a
AG4A, AS4A (20 µeq, NaHCO3 (15 mM)
− − − 2− − UV + suppressed
F , Cl , Br , SO4 , I , BD 15) AG5, AS5 1 NaHCO3, Na2CO3
conductivity
Na+, K+, Mg2+, Ca2+ (20 µeq, BD 15, LD 120) (1.7 mM, 1.8 mM) a [15]
Suppressed
Mineral waters AG12, CS12 1 (2.8 meq, Methanesulphonic
conductivity
BD 8) (Dionex, IonPac) Acid (20 mM) b
Na benzoate (0.5 mM),
−
Cl , NO3 , SO42−,
−
Na , + 2
Anionic Column Cationic Na citrate (0.1 mM) c
Non-suppressed
K , Mg , Ca , Sr2+,
+ 2+ 2+
Column 2 Cationic Column 2 HNO3 (0.1 mM) c Oxalic [16]
conductivity
Ba2+ Oil field water (Laboratory prepared, BD 5) acid (1.5 mM), ethylene
diamine (1.5 mM) c
F−, Cl−, Br−, NO3−, AG9-HC, AS9-HC 1
Na2CO3 (9 mM) b
SO42−, Na+, K+, Mg2+, (190 µeq, BD 9, LD 90) Suppressed
Methanesulphonic [17]
Ca2+, Sr2+ Sea, AG12A, CS12A 1 (2.8 meq, conductivity
Acid (20 mM) b
estuary water BD 8) (Dionex, IonPac)
Na+, K+, Mg2+, Ca2+ AG12A, CS12A 1 (2.8 meq, Suppressed
H2SO4 (8.25 mM) d [18]
Brine BD 8) (Dionex, IonPac) conductivity
Li+, Na+, NH4+, K+,
Mg2+, Ca2+, Sr2+ CS12A 1 (2.8 meq, BD 8) Methanesulphonic Suppressed
[19]
Eutrophic sea, fish (Dionex, IonPac) acid (18 mM) b conductivity
otoliths (+Mn2+)
1
Notes: BD, Bead diameter/µm; LD, Latex diameter/nm; mM, mmol/L; Column size, I. D. × Length = (4 × 250) mm;
2
Column size, I. D. × Length = (4.6 × 100) mm; Flow rate = 2 mL/min; Flow rate = 1 mL/min; c Flow rate = 1.5 mL/min;
a b

d
Flow rate = 1.2 mL/min.

Determination of Cl−, NO3−, SO42−, Na+, K+, Mg2+, Ca2+, Sr2+ and Ba2+ in oilfield water was made
possible by three runs under the conditions specified in Table 1. The anionic and the cationic column
were prepared in the laboratory by chemically modifying 5 μm silica beads. The anionic exchange
functionality was achieved by using γ-chloropropyl triethoxy silane, hexamethyl disilazane and
N,N-dimethyl benzylamine, phenyl trichlorosilane, chlorosulfonic acid and hexamethyl disilazane were
used to obtain the cationic exchange functionality. A good agreement with the results obtained with
other conventional methods was confirmed [16]. Typical chromatograms of a sample are in the
original publication presented in Figure 2.
Concentrations of F−, Cl−, Br, NO3, SO42−, Na+, K+, Mg2+, Ca2+ and Sr2+ in seawater and derived
saline solutions were determined in two single IC runs, one for anions and another one for cations
Water 2013, 5 664

(Table 1) and the results so obtained were critically assessed in terms of anion-cation balance and
further related to conductivity and salinity measurements aiming to evaluate the quality/completeness
of ion chromatographic analyses and to search for other meaningful relations for efficient
recognition/distinction between saline solutions of different types [17]. Typical chromatograms of the
samples are in the original publication presented in Figure 3.

3.1.2. Cations

Even though lithium, sodium, ammonium, potassium, rubidium, caesium, calcium, magnesium and
strontium were confirmed to be well separated with a gradient elution program the concentrations of
Na+, K+, Mg2+ and Ca2+ were later successfully determined in brine samples under isocratic conditions
(Table 1) in 1 µL injection volumes which required only minimal dilution and for which good
recoveries were confirmed [18].
By successfully determining Li+, Na+, NH4+, K+, Mg2+, Ca2+, Sr2+ in coastal, off-shore and sediment
waters and Mn2+ and other already mentioned cations in fish otoliths (Table 1) in the Adriatic Sea and
the Canal of Sicily the authors enabled an insight into relation between fish growth and environmental
conditions. By observing higher strontium concentrations in coastal waters than off-shore and
recognizing a decrease in the Sr/Ca ratio with increasing weight of the otolith they confirmed the
hypothesis that juveniles grow in proximity to eutrophic coastline waters [19]. Typical chromatograms
of the samples are in the original publication presented in Figures 2 and 3.

3.2. Selected Anions

Among all ion chromatographic analyses of waters with a high ionic strength, the determinations of
iodide concentration received the highest attention. An overview comprising the most essential
experimental conditions is summarized in Table 2 and continues with the applications in which iodide
was determined simultaneously with other anions, and further proceeds with the determinations of
bromide as a single ion and ends with bromide and bromate. Another group of related applications,
which are summarized in Table 3, is dedicated to nutrients: nitrate, nitrite and phospahate. Methods for
ion chromatographic determinations of thiosulfate and polythionates; and perchlorate are described
under separate headings at the end of this section and are not included in tables.

Table 2. Ion chromatographic determinations of iodide or bromide, alone or

simultaneously with some other ions in waters with high ionic strength.
Analyte,
Column Eluent Detection Ref.
Sample
Methanesulphonic acid
0.4 mL/L), NaCl
Post-column derivatization:
− 1 (5.84 g/L),
I Saline AS11 (45 µeq, BD 13, LD N-chlorosuccinimide,
4,4'-bis(dimethylamino)- [20]
(untreated) 85) (Dionex, IonPac) succinimide, succinate
diphenylmethane
buffer VIS λ = 605 nm
(0.8 g/L), Methanol
(200 mL/L), water a
Water 2013, 5 665

Table 2. Cont.
Analyte,
Column Eluent Detection Ref.
Sample
AG4A-SC, AS4A-SC 1
I−, Sea water
(20 µeq, BD 13, LD 160) NaOH (100 mM) b UV λ = 226 nm [21]
(untreated)
(Dionex, IonPac)
Semi-microcolumn 2 NaClO4 (30 mM), NaCl (500
I− Sea water
Stationary phase: TSKgel mM), sodium phosphate
(untreated, UV λ = 226 nm [22]
SAX (Tosoh) (3.7 meq/g, buffer pH 6.0
2 mL)
BD 5) (5 mM) c
NaClO4 (0.2 mM)
I−, Sea water Zwittergent-3-14 modified
Zwittergent-3-14 UV λ =210 nm [23]
(untreated) ODS column 3 (BD 5)
(0.3 mM) c
Microcolumn 4: PEG/C30
I− Sea water Na2SO4 (500 mM), NaCl (50
binary (BD 5) (Laboratory UV λ = 220 nm [24]
(untreated) mM) d
prepared)
Microcolumn 4:
I˗ Sea water Polyoxyethylene oleyl ether
NaCl (300 mM) d UV λ = 220 nm [25]
(untreated) modified C30 (BD 5)
(Laboratory prepared)
I−, IO3− Sea G3154A/102,
NH4NO3 (20 mM),
water G3154A/101 5 (50 µeq/g, ICP-MS [26]
pH 5.6 c
(diluted) BD 10) (Agilent)
I−, Br−, SO42−
AG9-SC, AS9-SC 1 ((30 to
Oilfield
35) µeq, BD 13, LD 110) Na2CO3 (3 mM) e Suppressed conductivity [27]
waters
(Dionex, IonPac)
(diluted)
I−, Br−, NO3− Zwittergent-3-14 modified Diluted artificial sea
UV λ = 210 nm [28]
Sea water ODS 3 water c
Br− Sea water Zwittergent-3-14 modified UV λ = 220 nm Non-
Pure water c [29]
(untreated) ODS 3 suppressed conductivity
Cetyltrimethylammonium ion
NaCl (500 mM),
Br− Sea water modified monolithic silica
cetyltrimethylammonium UV λ = 210 nm [30]
(untreated) capillary columns 6
chloride (0.1 mM) f
(Laboratory prepared)
Br−, BrO3− G3154A/101 (guard,
NH4NO3 (20 mM),
Sea water separation column 5, ICP-MS [31]
pH 5.8 c
(diluted) 50 µeq/g, BD 10 (Agilent)
Notes: BD, Bead diameter/µm; LD, Latex diameter/nm; mM, mmol/L; 1 Column size, I. D. × Length = (4 × 250) mm;
2 3 4
Column size, I. D. × Length = (1 × 35) mm; Column size, I. D. × Length = (4.6 × 250) mm; Column size,
5 6
I. D. × Length = (0.32 × 100) mm; Column size, I. D. × Length = (4.6 × 150) mm; Column size, I. D. × Length =
(0.1 × 200) mm; Flow rate = 0.9 mL/min; Flow rate = 1.5 mL/min; Flow rate = 1 mL/min; d Flow rate = 2.1 µL/min;
a b c

e
Flow rate = 2 mL/min; f Flow rate = 5.6 µL/min.
Water 2013, 5 666

Table 3. Ion chromatographic determinations of concentrations of nutrients in samples

with high ionic strength.
Analyte, Sample Column Eluent Detection Ref.
−
NO3 , KCl soil Hamilton PRP X-100
KCl (1000 mM) a UV λ =210 nm [32]
extracts (diluted) (Hamilton)
Cetyltrimethylammonium
chloride coated ODS
NaCl (500 mM), sodium
NO3−, NO2− Sea monolithic columns
phosphate buffer UV λ =225 nm [33]
water (untreated) Chromolith Speed ROD
(5 mM) pH 4.7 b
RP-18e 1, Chromolith
RP-18e 2 (Merck)
NO3−, NO2−, PO43− AG9-HC, AG9-HC3, Valve NaHCO3, Na2CO3 (3 mM,
Suppressed conductivity
Estuary water AS9-HC 3 (190 µeq, BD 9, 14 mM) c (elute-off) [34]
UV λ =225 nm
(untreated) LD 90) (Dionex, IonPac) Na2CO3 (9 mM) c (elute)
NO3−, NO2−, PO43−
Metrosep ASUPP7-250 3 Suppressed conductivity
Saline Aquarium Na2CO3 (3.5 mM) d [35]
(108 µeq, BD 5) (Metrohm) UV λ =215 nm
water
NO3−, PO43− AG4A-SC, AS4A-SC3
NaHCO3, Na2CO3 Suppressed conductivity
Estuary water (20 µeq, BD13, LD 160) [36]
(0.765 mM, 0.81 mM) a UV λ = 210 nm
(untreated) (Dionex, IonPac)
NaHCO3, Na2CO3 (Two
NO3−, PO43− AG4A, AG4A, Valve compositions,
Marine sediment AS4A-SC 3 (20 µeq, BD13, elute-off/elute) 1.4 mM, Suppressed conductivity [37]
pore water LD 160) (Dionex, IonPac) pH 9.16 and 20 mM,
pH 9.5) b
PO43− Sea water ICE-AS1 4 (27 meq, BD 7.5)
HCl (50 mM ) e ICP-MS [38]
(untreated) (Dionex, IonPac)
1
Notes: BD, Bead diameter/μm; LD, Latex diameter/nm; mM, mmol/L; Column size, I. D. × Length = (4.6 × 50) mm;
2
Column size, I. D. × Length = (4.6 × 100) mm; Column size, I. D. × Length = (4 × 250) mm; 4 Column size, I. D. × Length
3

a b c d
= (9 × 250) mm; Flow rate = 2.0 mL/min; Flow rate = 3.0 mL/min; Flow rate = 1.0 mL/min; Flow rate =
e
0.7 mL/min; Flow rate = 1.2 mL/min.

3.2.1. Iodide

The first six papers listed in Table 2 describe methods for determining iodide in untreated sea water
samples [20–25]. Brandao et al. [20] used a post-column derivatization with N-chlorosuccinimide
followed by a spectrometric detection at the wavelength 605 nm; in contrast to other authors who
reported a direct spectrometric detection of iodide at the wavelengths between 210 and 226 nm.
Typical chromatogram of a sample is in the original publication presented in Figure 2. Several
methods share a similar approach for minimizing the interfering effect of chloride on the determination
of iodide. This is most commonly resolved so that sodium chloride is one of the eluent
components [20,22,24] or a sole eluent component [25]. In contrast to this approach Hu et al.
prevented the interfering effect of chloride by reducing its affinity towards the stationary phase, by the
technique termed electrostatic ion chromatography (EIC), in which zwitterionic surfactant layer is
applied on the stationary phase and the zwitterionic surfactant was also present in the eluent [23].
Water 2013, 5 667

Typical chromatograms of an unspiked and spiked sample are in the original publication presented in
Figure 1. Ito used a large 2 mL sample injection volume and proved that by replacing a macrocolumn
with a semi-microcolumn with an I.D. 1 mm the method sensitivity increased 2.8-fold [22]. Typical
chromatogram of a sample is in the original publication presented in Figure 5. Rong et al. successfully
used two different in house prepared microcolumns with an I. D. 0.32 mm for determining iodide in
sea water [24,25]. Typical chromatograms of the samples are in the original publications presented in
Figure 6 and 4, respectively. Limits of detection (S/N = 3) reported for iodide in different papers were
0.2 µg/L [22],0.8 ppb [20], 0.011 µmol/L [23], 13 µg/L [24] and 19 µg/L [25], respectively.
Chandramouleeswaran et al. achieved the recoveries of iodide higher than 98% [21], Ito reported the
recoveries 98.4% or 97.0% for a 2 mg/L or 5 mg/L iodide addition, respectively [22].

3.2.2. Iodide and Iodate

Linear plots were obtained in a concentration range (5.0 to 500) µg/L and the detection limits 1.5 µg/L
and 2.0 µg/L were achieved for a simultaneous determination of iodate and iodide in seawater,
respectively with a non-suppressed ion chromatographic method with inductively coupled plasma mass
spectrometric detection (ICP-MS). An anion-exchange column (G3154A/101, Agilent) and an
NH4NO3 eluent at the pH 5.6 were used. The recoveries for iodate and iodide were 101.3% ± 1.8% and
97.2% ± 2.3%, respectively [26].

3.2.3. Iodide, Bromide and Sulfate

Bromide, iodide and sulfate are very important for the characterization of oilfield waters. An
Dionex IonPac AS9-SC analytical column, sodium carbonate eluent and a suppressed conductometric
detection were used and the limits of detection 0.1 mg/L for bromide and sulfate and 0.2 mg/L for
iodide were achieved [27] Typical chromatograms of the samples are in the original publication
presented in Figures 3 and 4.

3.2.4. Iodide, Bromide and Nitrate

An octadecylsilica column modified with a zwitterionic surfactant [3-(N,N-dimethylmyristylammonio)

propanesulfonate] and a diluted artificial sea water as the eluent were used for simultaneous
determination of iodide, bromide and nitrate in sea water with spectrometric detection at the
wavelength 210 nm. Limits of detection were 0.75 µg/L for bromide, 0.52 µg/L for nitrate, and
0.8 µg/L for iodide [28]. Typical chromatogram of a sample is in the original publication presented
in Figure 5.

3.2.5. Bromide

The concentration of bromide was directly determined in sea water with EIC with spectrometric and
conductometric detection, the results obtained with this method were 0.059 mmol/L ± 1.0% and
0.057 mmol/L ± 0.94%, and were comparable with the results of IC. The zwitterionic surfactants
immobilized on octadecylsilica surfaces acted as the stationary phase and water was used as the mobile
Water 2013, 5 668

phase [29]. Typical chromatograms of the samples are in the original publication presented in
Figures 5 and 6.
Monolithic silica capillary columns, which were prepared with a sol–gel method, were dynamically
modified with cetyltrimethylammonium ion and enabled a determination of 63 mg/L of bromide in
20 nL of untreated sea water sample. The eluent contained NaCl and cetyltrimethylammonium chloride
(CTAC). Spectrometric detection was performed at the wavelength 210 nm [30]. Typical
chromatogram of a sample is in the original publication presented in Figure 4.

3.2.6. Bromide and Bromate

An ion chromatographic method employing a G3154A/101 guard and separation column (Agilent),
NH4NO3 eluent at pH 5.8 and ICP-MS detection was developed, which enabled a direct determination
of bromate and bromide in a diluted sea water sample with a limit of detection which ranged from
(2.0 to 3.0) μg/L [31]. Typical chromatogram of a sample is in the original publication presented in
Figure 2.

3.2.7. Nitrate

Nitrate was successfully determined in KCl soil extracts with ion chromatography employing KCl
solution as an eluent and performing a spectrometric detection at the wavelength 210 nm. Bromide
interference was avoided by spiking the diluted soil extracts with a constant amount of nitrate, which
shifted a bromide nitrate ratio so that bromide did not interfere any more, and consequently nitrate was
reliably determined in concentrations down to 25 µg/L [32].

3.2.8. Nitrite and Nitrate

Nitrite and nitrate were well resolved and eluted within three minutes from the CTAC modified
monolithic ODS columns and successfully determined in untreated sea water in concentrations
(10.8 ± 0.5) µg/L, and (21.3 ± 0.5) µg/L if the NaCl, sodium phosphate buffer eluent was used and
spectrometric detection was performed at the wavelength 225 nm. The limits of detection (S/N = 3) for
nitrite and nitrate were 0.8 μg/L and 1.6 µg/L, respectively [33]. Typical chromatogram of a sample is
in the original publication presented in Figure 3.

3.2.9. Nitrate, Nitrite and Phosphate

For nitrate, nitrite and phosphate the limits of detection (0.1, 0.3 and 1) mg/L were achieved,
respectively with the suppressed conductometric and spectrometric detection in series at the
wavelength 225 nm. Chloride was eliminated with a column-switching method. Nitrate at the
concentration level 5 mg/L was successfully determined in an estuary water, while nitrite and
phosphate were undetectable [34]. Typical chromatogram of a sample is in the original publication
presented in Figure 5.
Nitrate-N, nitrite-N and phosphate-P were successfully determined in saline aquarium water in
concentrations as low as (0.026, 0.021 and 0.04) mg/L, respectively with the suppressed conductometric
Water 2013, 5 669

and spectrometric detection at the wavelength 215 nm. Concentrations of these anions in sea water
were below the limits of detection [35].

3.2.10. Nitrate and Phosphate

An ion chromatographic method using spectrometric detection at the wavelength 210 nm for nitrate
determination and suppressed conductometric detection for phosphate determination was reported. A
limit of detection for phosphate in sea water was proved to be 0.1 mg/L and this ion was successfully
determined in the estuary waters in concentrations between 0.3 and 1.6 mg/L during the winter months
when salinity was lower due to dilution caused by the rainfall, and the nutrients were more intensively
supplied by the in-coming streams. Concentration of nitrate between 0.3 and 11.1 mg/L were determined
in the samples and the limit of detection was found out to be 0.04 mg/L [36]. Typical chromatogram of
a sample is in the original publication presented in Figure 3.
The 0.5 µmol/L and 1 µmol/L limits of detections were achieved for nitrate and phosphate
determination in the marine sediment pore water with an ion chromatographic method with suppressed
conductometric detection. Experimental conditions defined by six factors were optimized using a
fractional factorial experimental design. A column-switching method was used for reducing the
chloride interference effect [37]. Typical chromatogram of a sample is in the original publication
presented in Figure 6.

3.2.11. Phosphate

The 0.06 µmol/L limit of detection (3s) was achieved with ion-exclusion chromatography with ICP-MS
detection for phosphate determination in untreated sea water. The concentration of dissolved phosphate
determined in sea-water with this ion chromatographic method (1.69 ± 0.04) µmol/L is in good
agreement with the result of the colorimetric procedure (1.71 ± 0.04) µmol/L [38]. Typical
chromatogram of a sample is in the original publication presented in Figure 4.

3.2.12. Thiosulfate and Polythionates

A pre-concentration technique using an ion-exchange pre-column and a reversed phase analytical

column in series and a water-acetonitrile eluent containing tetrabutylammonium ions and carbonate
buffer was developed for determining thiosulfate and polythionates in natural saline waters. Limits of
detection achieved with a pre-concentration of 6 mL of 50-times diluted seawater were: 1 nmol/L for
trithionate, and 0.3 nmol/L for tetrathionate and pentathionate [39].

3.2.13. Perchlorate

The limit of detection 0.77 µg/L (S/N = 3) was reported for an ion chromatographic method
intended for perchlorate determination in waters of different conductivities ranging up to 14.7 mS/cm.
With a pre-concentration of a 2 mL sample volume and elimination of interfering ions by
column-switching, higher recoveries of perchlorate ion were achieved than with the recommended
EPA Method [40].
Water 2013, 5 670

3.3. Selected Cations

The more comprehensive ion chromatographic determinations of cations closer matching the total
cationic composition of water samples were presented in Section 1.1. Here we present methods that
focus on determinations of selected cations or a single cation. The main experimental conditions
defining these methods are summarized in Table 4.

Table 4. Ion chromatographic determinations of concentrations of selected cations in

waters with high ionic strength.
Analyte, Sample Column Eluent Detection Ref.
Ethylenediamine
Mg2+, Ca2+, Sr2+ Brine, Suppressed
CG-2, CS-2 (Dionex, IonPac) (2.5 mM),HCl (5 mM), zinc [41]
Sea water (diluted) conductivity
acetate (1 mM)
high-speed cationic column Ethylenediamine (0.5 mM), Non-suppressed
Sr2+ Sea water (diluted) [42]
(Cat.no.269-25, Wescan) oxalic acid (0.5 mM), pH 6 a conductivity
CG-12A Valve CS-12A1 (2800 µeq, Suppressed
NH4+ Sea water(diluted) H2SO4 (25 mM) b [43]
BD 8) (Dionex, IonPac) conductivity
NH4+ Sea water CG-16A CS-16A2 (8400 µeq, BD 5) Methanesulphonic Acid Suppressed
[44]
(purge-and-trap) (Dionex, IonPac) (45 mM) b conductivity
1
Notes: BD, Bead diameter/μm; LD, Latex diameter/nm; mM, mmol/L; Column size, I. D. × Length = (4 × 250) mm;
2 a b
Column size, I. D. × Length = (5 × 250) mm; Flow rate = 1.2 mL/min; Flow rate = 1 mL/min.

3.3.1. Magnesium, Calcium and Strontium

Strontium, magnesium and calcium were successfully simultaneously determined in high salinity
sub-surface waters with ion chromatography with suppresses conductometric detection using an eluent
which comprised ethylenediamine, HCl and zinc acetate, and the results compared well with those
obtained with atomic absorption spectrometry [41].

3.3.2. Strontium

A non-suppressed ion chromatographic method with conductometric detection was developed for
determination of strontioum in coastal sea water and the results compared well with those obtained by
ICP-OES. The eluent comprised ethylenediamine and oxalic acid. The limit of detection for strontium
determination was found to be 1 mg/L [42]. Typical chromatogram of a sample is in the original
publication presented in Figure 5.

3.3.3. Ammonium

Ion chromatographic method, with suppressed conductometric detection and an on-line sample
pre-concentration with a column-switching, was developed for ammonium determination in sea water.
The limit of detection for ammonium ion in the presence of 1000 mg/L sodium was 12.8 µg/L. It was
proved that 90% of ammonium was introduced and concentrated if concentration was lower than
1 mg/L [43].Typical chromatogram of a sample is in the original publication presented in Figure 3.
Water 2013, 5 671

The 1.35 µg/L (75 nmol/L) limit of detection was confirmed for ammonium determination in sea
water samples with the approach that combined a purge-and-trap pre-concentration step with ion
chromatography with suppressed conductometric detection. A linear range for ammonium extended
from 50 nmol/L to 6.0 µmol/L [44]. Typical chromatogram of a sample is in the original publication
presented in Figure 7.

3.4. Metals

The main experimental conditions for ion chromatographic determinations of metals in samples
with high ionic strength are summarized in Table 5. Chelation ion chromatography as a
pre-concentration step in combination with spectrometric detection in the visible range after post-column
derivatization is most frequently reported. More details are given in continuation.

Table 5. Ion chromatographic determinations of concentrations of metals.

Analyte, Sample Column Eluent Detection Ref.
Zn, Pb, Ni, Cu Sea Xylenol Orange-impregnated KNO3 (500 mM), Post-column derivatization:
water, CASS-2 coastal polystyrene-divinylbenzene lactic acid (50 mM), Pyridyl-azo-resorcinol, NH3,
[45]
sea-water certified neutral PLPRS resin (Polymer pH adjustment NH3 or NH4NO3 pH 10.2 VIS
reference material Laboratories) (BD 5) HNO3 a λ = (490 to 520) nm
Cu, Ni, Zn, Co MetPac-CC1 (iminodiacetate Pyridine-2,
Reference materials chelating concentrator column) 6-dicarboxylic acid Post-column derivatization:
for trace metals CG5, CS5 1 (BD 13, LD 110, (6 mM), acetate buffer Pyridyl-azo-resorcinolNH3,
[46]
estuarine water 150 μeq sulfonic, 70 μeq CH3COOH, (50 mM), CH3COOH, pH 9.7 VIS
(SLEW-2) (diluted, alkanol quaternary ammonium) CH3COONa (50 mM), λ = 520 nm
pH 3) (Dionex, IonPac) pH 4.5 a
AS10, AS10 1 (170 µeq, BD
Selenium species 8.5, LD 65) AG11, AS11 1 Na2CO3 (10 mM) a
ICP-AES [47]
Artificial sea water (45 µeq, BD 13, LD 85) NaOH (10 mM) a
(Dionex, IonPac)
N-methyl-γ-amino-
butyrohydroxamate resin guard
Post-column derivatization:
La, Ce, Pr, Nd, Sm, and concentrator column 2, Oxalic acid (30 mM,
4(2-pyridylazo)resorcinol
Eu, Gd, Tb, Dy, Ho, (1.5 to l.9) mM/g CS5 3(BD 13, pH 4.5), diglycolic [48]
ZnEDTA, NH3, NH4Cl, pH
Er Sea water LD 110, 150 μeq sulfonic, acid (5 mM)
10, VIS λ = 495 nm
70 μeq alkanol quaternary
ammonium) (Dionex, IonPac)
Mn, Co, Ni, Cu, Zn,
Nitrilotriacetate (NTA)-type
No, Cd, Sb, Pb, U
chelating poly KNO3 (500 mM) a ICP-MS [49]
Sea-Water Ref.
(styrene-divinylbenzene) resin 4
Material NASS-4
Post-column deriv.: chrome
Iminodiacetic acid KNO3 (400 mM), azurol S, Triton X-100,
Be Artificial sea water functionalised silica gel adjusted to pH 2.5 2-(N-morpholino) [50]
(Bio-ChemMack) (BD 8)1 using HNO3 a ethane-sulfonic acid, pH 6.0,
VIS λ = 590 nm
Water 2013, 5 672

Table 5. Cont.
Analyte, Sample Column Eluent Detection Ref.
Chelated
polystyrene-divinylbenzene
resins: BAETM (bis
V, Mo, W Artificial (2-aminoethylthio) methylated)
5 HNO3 pH 1.5 a ICP-MS [51]
sea water Chelated acrylonitrile and
divinylbenzene resin:
γ-ABHX
(γ-aminobutyrohydroxamate) 6
Post-column derivatiz.: borate
Aurin tricarboxylic acid
Cd, Pb, Cu Mineral KNO3 (100 mM) buffer,
impregnated polystyrene [52]
waters pH gradient 1 4-(2-pyridylazo)resorcinol VIS
divinylbenzene resin 3 (BD 7)
λ = 520 nm
1
Notes: BD, Bead diameter/μm; LD, Latex diameter/nm; mM, mmol/L; Column size, I. D. × Length = (4 × 250) mm;
2 3 4
Column size, I. D. × Length = (2 × 50) mm; Column size, I. D. × Length = (4.6 × 250) mm; Column size,
5 6
I. D. × Length = (4.6 × 50) mm; Column size, I. D. × Length = (4 × 50) mm; Column size, I. D. × Length = (6 × 30) mm;
a
Flow rate = 1 mL/min.

Low µg/L levels of Zn-II, Pb-II, Ni-II and Cu-II were determined in CASS-2 coastal sea-water
certified reference material with chelation ion chromatography with a pre-concentration and separation
on a Xylenol Orange-impregnated resin, and spectrometric detection in the visible range after post-column
derivatization [45]. Typical chromatograms of the samples are in the original publication presented in
Figures 1 and 2.
The limits of detection 0.025 µg/L, 0.036 µg/L, 0.064 µg/L and 0.022 µg/L were achieved for
copper, nickel, zinc and cobalt, respectively with a pre-concentration of a 25 mL-sample on an
iminodiacetate chelating column. Desorption from the concentrator column and separation in an ion
exchange column was achieved with an eluent containing pyridine-2,6-dicarboxylic acid in acetate
buffer. Detection was spectrometric in the visible range after post-column derivatization, samples had
to be diluted and pH set to 3. The reference material for trace metals in estuarine water (SLEW-2) was
successfully analysed [46]. Typical chromatograms of the samples are in the original publication
presented in Figure 8.
Inorganic and amino acid forms of selenium were determined by ion chromatography with
inductively coupled plasma atomic emission spectroscopic (ICP-AES) detection. Three different
columns were tested. The columns AS10 and AS11 (Dionex) both proved useful, but limits of
detection were lower for the later and ranged between 0.32 mg/L (Se-methionine) and 0.62 mg/L
(Se-cystine) and were close to 0.5 mg/L for HSeO3− and HSeO42− [47]. Typical chromatograms of the
samples are in the original publication presented in Figures 1 and 2.
The 2.5 μg/L detection limit was achieved for the determination of lanthanides in sea water by a
pre-concentration of 25 mL of sea water on a chelation stationary phase followed by ion
chromatographic separation and spectrometric detection in the visible range after a post-column
derivatization [48]. Typical chromatogram of a sample is in the original publication presented
in Figure 5.
Water 2013, 5 673

The results of the determination of the concentrations of metals (Mn, Co, Ni, Cu, Zn, No, Cd, Sb,
Pb and U) in the Open Ocean Sea-Water Reference Material NASS-4 obtained with a chelation ion
chromatographic method with ICP-MS detection were in good agreement with the certified values.
With the efficient preconcentration and simultaneous matrix elimination, the detection limits ranged
from 4 ng/L for Cu to 0.7 µg/L for Mo [49].
Beryllium was successfully determined in artificial sea water using an iminodiacetic acid
functionalized silica gel column and spectrometric detection in the visible range after a post-column
derivatization. Detection limits for Be(II) in a standard solution and a typical tap water sample were 3 μg/L
and 4 µg/L, respectively [50]. Typical chromatograms of the samples are in the original publication
presented in Figures 5 and 6. Two kinds of chelating resin, bis (2-aminoethylthio) methylated resin
(BAETM) and gamma-aminobutyrohydroxamate resin (gamma-ABHX) were synthesized and tested.
The detection limit 0.01 µg/L was achieved for the determination of vanadium, molybdenum and
tungsten with a BAETM resin column. The γ-ABHX resin column demonstrated efficient separation
between target metals and sea water matrix cations [51]. Typical chromatogram of a sample is in the
original publication presented in Figure 7.
Metal ions Cd (II), Pb (II) and Cu (II) were baseline separated from other transition metals and the
alkaline earth metals within 30 min and their concentrations determined in highly mineralized water
with a chromatographic system comprising aurin tricarboxylic acid impregnated polystyrene
divinylbenzene resin, pH gradien elution and post-column derivatization with spectrometric detection
in the visible range. The limits of detection were 1 µg/L for Cd (II) and 5 µg/L for both Pb (II) and
Cu (II),respectively [52]. Typical chromatogram of a sample is in the original publication presented in
Figure 7.

4. Conclusions

Even though ion chromatography is four decades after its introduction in the mid-seventies a
well-established analytical technique with very many applications, it can be concluded that
applications dedicated to analyses of natural waters with high ionic strength are not so numerous,
confirming that they still represent an analytical challenge. Less frequent are applications targeting the
determination of the total ionic composition of highly mineralized waters with ion chromatography as
completely as possible, and those trying to master ion chromatographic analyses of highly mineralized
waters of different types.

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